JP5354338B2 - Amino group-containing particles, method for producing the same, and functional product containing the particles - Google Patents
Amino group-containing particles, method for producing the same, and functional product containing the particles Download PDFInfo
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本発明は、アミノ基含有粒子に関する。詳細には、ニトリル基を含有する重合体からなる粒子とアミノ基含有有機化合物とを反応させることで、架橋構造とアミノ基を同時に導入して得られるアミノ基含有粒子に関する。 The present invention relates to amino group-containing particles. Specifically, the present invention relates to amino group-containing particles obtained by simultaneously introducing a crosslinked structure and an amino group by reacting particles comprising a polymer containing a nitrile group with an amino group-containing organic compound.
従来より、さまざまな製品に特定の機能を付加する目的で、該製品の製造中あるいは製造後に機能性を有する粒子を付与し、目的とする機能の発現を達成しようとする試みが多くなされている。 Conventionally, for the purpose of adding a specific function to various products, many attempts have been made to achieve the expression of the target function by imparting functional particles during or after the manufacture of the product. .
かかる目的に利用される機能性粒子としては、例えば、ヒドラジン架橋を有するアクリロニトリル系重合体微粒子に塩型カルボキシル基を導入して得られる吸放湿性微粒子（特許文献１）やイオン交換またはイオン配位可能な極性基を含有する架橋ポリマー粒子中に金属超微粒子や金属錯体超微粒子を含有させた抗菌・抗黴ポリマー粒子（特許文献２）などが知られている。しかし、前者の粒子は、架橋導入し、その後加水分解によってカルボキシル基を導入し、さらにカルボキシル基の塩型を調整するという製造工程を有し、後者の粒子は該製造工程に加え、金属イオンを導入し、還元するという工程を有するものであり、多くの製造工程を経なければ得ることができない。また、これらの粒子はヒドラジン架橋や金属微粒子を含有するため、着色しており、経時による変色も起こりやすい。 Examples of the functional particles used for this purpose include hygroscopic fine particles (Patent Document 1) obtained by introducing a salt-type carboxyl group into acrylonitrile-based polymer fine particles having hydrazine bridge, ion exchange or ion coordination. Antibacterial / antifungal polymer particles (Patent Document 2) in which metal ultrafine particles or metal complex ultrafine particles are contained in crosslinked polymer particles containing possible polar groups are known. However, the former particles have a production process in which cross-linking is introduced, carboxyl groups are then introduced by hydrolysis, and the salt type of the carboxyl groups is further adjusted, and the latter particles have metal ions added in addition to the production process. It has a process of introducing and reducing, and it cannot be obtained unless it goes through many manufacturing processes. In addition, these particles are colored because they contain hydrazine bridges and metal fine particles, and discoloration with time is likely to occur.
また、特許文献３には、アミノ基を利用した酸・アルデヒド吸収性を有する重合体が開示されており、アミノ基の導入方法について、ヒドラジンで高ニトリル系重合体を処理し、架橋構造とアミン構造を同時に導入することが好ましいとされている。しかし、かかる方法では、窒素含有官能基は多量に導入できるものの、アルキル基やアルキレン基などの電子供与的性質を有する基と結合したアミノ基は導入されず、一般的な弱塩基性陰イオン交換樹脂よりも塩基性が弱くなり、加えて架橋構造も短く、密となる。このため、測定値としてのアニオン交換容量は高いものの、実際の酸・アルデヒド吸収性能としてはそれほど高いものとならない。 Patent Document 3 discloses an acid / aldehyde-absorbing polymer utilizing amino groups. Regarding the method of introducing amino groups, a high nitrile polymer is treated with hydrazine to form a crosslinked structure and an amine. It is preferred to introduce the structure simultaneously. However, in this method, although a nitrogen-containing functional group can be introduced in a large amount, an amino group bonded to a group having an electron donating property such as an alkyl group or an alkylene group is not introduced, and general weak basic anion exchange is not performed. The basicity is weaker than that of the resin, and in addition, the cross-linked structure is short and dense. For this reason, the anion exchange capacity as a measured value is high, but the actual acid / aldehyde absorption performance is not so high.
本発明者は、かかる事情に鑑み、鋭意検討を進めた結果、ニトリル基を含有する重合体からなる粒子を特定のアミノ基含有有機化合物で処理することによって粒子中に架橋構造とアミノ基を同時かつ効率的に導入でき、得られた粒子が優れた性能を有することを見出し本発明に到達した。本発明の目的は、ニトリル基を含有する重合体からなる粒子を改質して得られる優れた機能を有する粒子および該粒子の効率的な製造方法ならびに該粒子を含む機能性製品を提供することにある。 In view of such circumstances, the present inventor has intensively studied, and as a result, by treating particles comprising a polymer containing a nitrile group with a specific amino group-containing organic compound, the crosslinked structure and the amino group are simultaneously contained in the particles. The present invention has been found out that the particles can be introduced efficiently and the obtained particles have excellent performance. An object of the present invention is to provide particles having an excellent function obtained by modifying particles made of a polymer containing a nitrile group, an efficient method for producing the particles, and a functional product containing the particles. It is in.
本発明の上記目的は、以下の手段により達成される。すなわち、
［１］ニトリル基を含有し、架橋構造を含有しない重合体からなる粒子を１分子中の全アミノ基数が３以上であり、かつ、１級アミノ基数が２以上であって、アミノ基間を炭素数が３以上のアルキレン基で結合した構造を有するアミノ基含有有機化合物で処理することによって粒子中に架橋構造とアミノ基を同時に導入して得られるアミノ基含有粒子。
［２］アミノ基量が０．１ｍｍｏｌ／ｇ以上であることを特徴とする［１］に記載のアミノ基含有粒子。
［３］２０℃６５％ＲＨにおける飽和吸湿率が１５質量％以上であることを特徴とする［１］または［２］に記載のアミノ基含有粒子。
［４］２０℃９５％ＲＨおよび２０℃５０％ＲＨにおける飽和吸湿率の差が５０パーセントポイント以上であることを特徴とする［１］〜［３］のいずれかに記載のアミノ基含有粒子。
［５］ニトリル基を含有し、架橋構造を含有しない重合体からなる粒子に１分子中の全アミノ基数が３以上であり、かつ、１級アミノ基数が２以上であって、アミノ基間を炭素数が３以上のアルキレン基で結合した構造を有するアミノ基含有有機化合物を反応させることによって粒子中に架橋構造とアミノ基を同時に導入することを特徴とするアミノ基含有粒子の製造方法。
［６］［１］〜［４］のいずれかに記載のアミノ基含有粒子を含む機能性製品。
The above object of the present invention is achieved by the following means. That is,
[1] Particles made of a polymer containing a nitrile group and not containing a crosslinked structure have a total number of amino groups of 3 or more in one molecule and a primary amino group number of 2 or more. Amino group-containing particles obtained by simultaneously introducing a crosslinked structure and an amino group into a particle by treating with an amino group-containing organic compound having a structure bonded with an alkylene group having 3 or more carbon atoms .
[ 2 ] The amino group-containing particles according to [1], wherein the amino group amount is 0.1 mmol / g or more.
[ 3 ] The amino group-containing particles according to [1] or [2] , wherein the saturated moisture absorption at 20 ° C. and 65% RH is 15% by mass or more.
[ 4 ] The amino group-containing particles according to any one of [1] to [ 3 ], wherein the difference in saturated moisture absorption at 20 ° C. 95% RH and 20 ° C. 50% RH is 50 percentage points or more.
[ 5 ] Particles made of a polymer containing a nitrile group and containing no cross-linked structure have 3 or more total amino groups in one molecule, 2 or more primary amino groups, A method for producing an amino group-containing particle, wherein a cross-linked structure and an amino group are simultaneously introduced into a particle by reacting an amino group-containing organic compound having a structure bonded with an alkylene group having 3 or more carbon atoms .
[ 6 ] A functional product containing the amino group-containing particles according to any one of [1] to [ 4 ].
本発明によれば、ニトリル基を含有する重合体からなる粒子に架橋構造とアミノ基を１工程で導入できるため、工程が簡略化でき、製造コストの低減、廃棄物の減少などが期待できる。また、得られる粒子は、導入されたアミノ基がアルキレン基に結合しているため良好な塩基性を示すものであり、従来技術のように改めて加水分解を行わなくても高い飽和吸湿率および飽和吸湿率差を発現するものであって、しかも着色の少ない粒子である。さらに、本発明のアミノ基含有粒子は良好な塩基性を示すアミノ基の作用により、優れた抗菌、抗かび、抗ウイルス性をも発現するものである。かかる本発明のアミノ基含有粒子は酸性ガス除去、水の脱塩、アニオン交換、吸湿、調湿、抗菌、抗かび、抗ウイルスなど、衣料分野も含め、様々な用途へ展開することができ、製品価格の低下などに寄与できるものである。 According to the present invention, since a crosslinked structure and an amino group can be introduced into particles composed of a polymer containing a nitrile group in one step, the steps can be simplified, and production cost reduction, waste reduction, and the like can be expected. In addition, the obtained particles exhibit good basicity because the introduced amino group is bonded to the alkylene group, and have a high saturated moisture absorption and saturation without re-hydrolysis as in the prior art. It is a particle that expresses a difference in moisture absorption and has little coloration. Furthermore, the amino group-containing particles of the present invention exhibit excellent antibacterial, antifungal, and antiviral properties due to the action of an amino group exhibiting good basicity. Such amino group-containing particles of the present invention can be developed for various uses including the clothing field, such as acid gas removal, water desalting, anion exchange, moisture absorption, humidity control, antibacterial, antifungal, antiviral, etc. It can contribute to lower product prices.
以下、本発明を詳述する。本発明のアミノ基含有粒子は、ニトリル基を含有する重合体からなる粒子を１分子中の全アミノ基数が３以上であり、かつ、１級アミノ基数が２以上であって、アミノ基間をアルキレン基で結合した構造を有するアミノ基含有有機化合物で処理することによって粒子中に架橋構造とアミノ基を同時に導入したものである。ここで、架橋構造は、親水性の高いアミノ基含有粒子が水に膨潤して粒子の形状が変化したり、強度が低下したりすることを抑制する効果があり、また、アミノ基はアニオン交換性能、吸湿性能、抗菌性能、抗かび性能あるいは抗ウイルス性能などの諸性能に寄与する。 The present invention is described in detail below. The amino group-containing particles of the present invention are particles comprising a polymer containing a nitrile group, wherein the total number of amino groups in one molecule is 3 or more, and the number of primary amino groups is 2 or more. By treating with an amino group-containing organic compound having a structure bonded with an alkylene group, a crosslinked structure and an amino group are simultaneously introduced into the particles. Here, the cross-linked structure has an effect of inhibiting the highly hydrophilic amino group-containing particles from being swollen in water and changing the shape of the particles or reducing the strength. Contributes to various performances such as performance, moisture absorption performance, antibacterial performance, antifungal performance and antiviral performance.
本発明に採用するニトリル基を含有する重合体からなる粒子としては、ニトリル基を含有するものであれば、特に制限はなく、例えば、ニトリル基を有するポリエステル、ポリアミド、ビニル系重合体などからなる粒子が挙げられる。特に、アクリロニトリル（以下ＡＮという）系重合体により形成された粒子は、効率よくニトリル基を含有させることができ、ニトリル基の量の調節も容易であるため、好ましく採用できる。 The particles composed of a polymer containing a nitrile group employed in the present invention are not particularly limited as long as they contain a nitrile group, and are composed of, for example, a polyester having a nitrile group, a polyamide, a vinyl polymer, or the like. Particles. In particular, particles formed of an acrylonitrile (hereinafter referred to as AN) polymer can be preferably employed because they can efficiently contain nitrile groups and the amount of nitrile groups can be easily adjusted.
かかるＡＮ系重合体としては、ＡＮ単独重合体あるいはＡＮと他の単量体との共重合体のいずれでも採用しうる。また、本発明において、アミノ基はニトリル基とアミノ基含有有機化合物の反応により導入されるので、ＡＮの共重合量が少なすぎる場合、導入されるアミノ基量が少なくなる。このため、ＡＮ共重合量としては、好ましくは４０質量％以上、より好ましくは５０質量％以上、さらに好ましくは８０質量％以上のとき良好な結果を得られやすい。 As the AN polymer, either an AN homopolymer or a copolymer of AN and another monomer can be adopted. In the present invention, since the amino group is introduced by the reaction of the nitrile group and the amino group-containing organic compound, when the amount of AN copolymerized is too small, the amount of amino group introduced is reduced. For this reason, when the AN copolymerization amount is preferably 40% by mass or more, more preferably 50% by mass or more, and still more preferably 80% by mass or more, good results are easily obtained.
ＡＮ系重合体としてＡＮと他の単量体との共重合体を採用する場合、ＡＮ以外の共重合成分としてはメタリルスルホン酸、ｐ−スチレンスルホン酸等のスルホン酸基含有単量体及びその塩、（メタ）アクリル酸、イタコン酸等のカルボン酸基含有単量体及びその塩、スチレン、酢酸ビニル、（メタ）アクリル酸エステル、（メタ）アクリルアミド等の単量体など、ＡＮと共重合可能な単量体であれば特に限定されない。ただし、高いアニオン交換性能が求められる場合には、酸性基を有する単量体の量は少ないほうが望ましい。 When a copolymer of AN and another monomer is employed as the AN polymer, the copolymer components other than AN include sulfonic acid group-containing monomers such as methallylsulfonic acid and p-styrenesulfonic acid, and the like. Its salts, carboxylic acid group-containing monomers such as (meth) acrylic acid and itaconic acid, and salts thereof, monomers such as styrene, vinyl acetate, (meth) acrylic acid ester, (meth) acrylamide, etc. There is no particular limitation as long as it is a polymerizable monomer. However, when high anion exchange performance is required, the amount of the monomer having an acidic group is preferably small.
また、かかるＡＮ系重合体により形成された粒子の製造手段としては特に制限はなく、乳化重合、懸濁重合、シード重合、分散重合などの公知の方法をそのまま適用して製造すればよい。 Moreover, there is no restriction | limiting in particular as a manufacturing method of the particle | grains formed with this AN type polymer, What is necessary is just to apply well-known methods, such as emulsion polymerization, suspension polymerization, seed polymerization, and dispersion polymerization, as it is.
また、粒子の大きさや形状に特に制限はなく、用途に応じて適宜選定することができる。平均粒子径が１０００μｍ以下、より好ましくは１００μｍ以下の微粒子状である場合、表面積が大きくなり、より多くのアミノ基が活用されるようになるので、アニオン交換速度、吸湿速度等の特性が向上し、より良好な結果を得ることができる。また、該粒子の形状も、球状、塊状、針状、棒状、紡錘状、円柱状など、特に制限はなく、ラテックスなどの粒子を水分散させた状態のものも好ましく採用できる。 Moreover, there is no restriction | limiting in particular in the magnitude | size and shape of particle | grains, According to a use, it can select suitably. In the case of fine particles having an average particle diameter of 1000 μm or less, more preferably 100 μm or less, the surface area becomes large and more amino groups are utilized, so that characteristics such as anion exchange rate and moisture absorption rate are improved. Better results can be obtained. Also, the shape of the particles is not particularly limited, such as a spherical shape, a lump shape, a needle shape, a rod shape, a spindle shape, or a cylindrical shape, and a particle in which particles such as latex are dispersed in water can be preferably employed.
本発明に採用するアミノ基含有有機化合物は、１分子中の全アミノ基数が３以上であり、かつ、１級アミノ基数が２以上であって、アミノ基間をアルキレン基で結合した構造を有するものである必要がある。かかるアミノ基含有有機化合物を用いることで、架橋構造とアミノ基を１工程で同時に導入することが可能となる。すなわち、該化合物中には１級アミノ基が２個以上あり、これらのアミノ基がニトリル基を含有する重合体からなる粒子のニトリル基と反応することにより該重合体間に架橋構造が形成される。そして、架橋反応で消費されなかった残りのアミノ基はそのまま該ニトリル基を含有する重合体からなる粒子に固定化され、アニオン交換性能や吸湿性能などが発現される。 The amino group-containing organic compound employed in the present invention has a structure in which the total number of amino groups in one molecule is 3 or more, the number of primary amino groups is 2 or more, and the amino groups are bonded by an alkylene group. It needs to be a thing. By using such an amino group-containing organic compound, it is possible to simultaneously introduce a crosslinked structure and an amino group in one step. That is, there are two or more primary amino groups in the compound, and these amino groups react with the nitrile groups of particles comprising a polymer containing a nitrile group to form a crosslinked structure between the polymers. The Then, the remaining amino groups that have not been consumed in the crosslinking reaction are fixed as they are to the particles made of the polymer containing the nitrile groups, and anion exchange performance, moisture absorption performance, and the like are exhibited.
ここで、アミノ基含有有機化合物において、全アミノ基数が３未満であると架橋反応に全てのアミノ基が消費され、十分なアニオン交換性能や吸湿性能が得られにくくなり、１級アミノ基数が２未満であると架橋構造が導入されにくくなる。また、アミノ基間をアルキレン基で結合した構造でない場合、アミノ基への電子供与が少なく、塩基性が不十分となって、アニオン交換性能などの性能が十分に得られない。 Here, in the amino group-containing organic compound, if the total number of amino groups is less than 3, all amino groups are consumed in the crosslinking reaction, and sufficient anion exchange performance and moisture absorption performance are difficult to obtain, and the number of primary amino groups is 2. If it is less than this, it becomes difficult to introduce a crosslinked structure. Further, when the structure is not a structure in which amino groups are bonded by an alkylene group, electron donation to the amino group is small, the basicity becomes insufficient, and performance such as anion exchange performance cannot be obtained sufficiently.
かかるアミノ基含有有機化合物の具体例としては、３，３’−イミノビス（プロピルアミン）、Ｎ−メチル−３，３’−イミノビス（プロピルアミン）、ラウリルイミノビスプロピルアミン、Ｎ，Ｎ’−ビス（３−アミノプロピル）エチレンジアミン、Ｎ，Ｎ’−ビス（３−アミノプロピル）−１，３−プロピレンジアミン、Ｎ，Ｎ’−ビス（３−アミノプロピル）−１，３−ブチレンジアミン、Ｎ，Ｎ’−ビス（３−アミノプロピル）−１，４−ブチレンジアミン、１，４−ビス（３−アミノプロピル）ピペラジン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンヘキサミン、ポリエチレンイミン、ポリビニルアミンなどのポリアミン類などが挙げられる。 Specific examples of such amino group-containing organic compounds include 3,3′-iminobis (propylamine), N-methyl-3,3′-iminobis (propylamine), lauryliminobispropylamine, N, N′-bis. (3-aminopropyl) ethylenediamine, N, N′-bis (3-aminopropyl) -1,3-propylenediamine, N, N′-bis (3-aminopropyl) -1,3-butylenediamine, N, Polyamines such as N′-bis (3-aminopropyl) -1,4-butylenediamine, 1,4-bis (3-aminopropyl) piperazine, diethylenetriamine, triethylenetetramine, tetraethylenehexamine, polyethyleneimine, and polyvinylamine Etc.
なかでも、３，３’−イミノビス（プロピルアミン）、Ｎ−メチル−３，３’−イミノビス（プロピルアミン）、ラウリルイミノビスプロピルアミン、Ｎ，Ｎ’−ビス（３−アミノプロピル）エチレンジアミン、Ｎ，Ｎ’−ビス（３−アミノプロピル）−１，３−プロピレンジアミン、Ｎ，Ｎ’−ビス（３−アミノプロピル）−１，３−ブチレンジアミン、Ｎ，Ｎ’−ビス（３−アミノプロピル）−１，４−ブチレンジアミン、１，４−ビス（３−アミノプロピル）ピペラジンなどのアミノ基間を炭素数が３以上のアルキレン基で結合した構造を有するアミノ基含有有機化合物はニトリル基を含有する重合体からなる粒子と反応速度が速く、コスト的に有利で好ましい。さらに、かかる構造を有するアミノ基含有有機化合物の場合、反応後の粒子を着色の少ないものにできる。なお、ここで言う炭素数とは、アミノ基を直接結ぶ炭素の数のことであって、分岐鎖や置換基などの炭素の数は含まない。なお、アミノ基間を炭素数が５以上のアルキレン基で結合した構造を有するアミノ基含有有機化合物は特殊で市場からの入手が困難であり、工業的に利用しにくい。 Among them, 3,3′-iminobis (propylamine), N-methyl-3,3′-iminobis (propylamine), lauryliminobispropylamine, N, N′-bis (3-aminopropyl) ethylenediamine, N , N′-bis (3-aminopropyl) -1,3-propylenediamine, N, N′-bis (3-aminopropyl) -1,3-butylenediamine, N, N′-bis (3-aminopropyl) ) -1,4-Butylenediamine, 1,4-bis (3-aminopropyl) piperazine and the like, an amino group-containing organic compound having a structure in which an amino group is bonded with an alkylene group having 3 or more carbon atoms has a nitrile group. The reaction rate of the particles made of the polymer to be contained is high, which is advantageous in terms of cost. Furthermore, in the case of an amino group-containing organic compound having such a structure, the particles after the reaction can be made less colored. The number of carbons referred to here is the number of carbons directly connecting amino groups, and does not include the number of carbons such as branched chains and substituents. An amino group-containing organic compound having a structure in which amino groups are bonded by an alkylene group having 5 or more carbon atoms is special and difficult to obtain from the market, and is difficult to use industrially.
抗菌性および抗かび性の観点からは、３，３’−イミノビス（プロピルアミン）やＮ−メチル−３，３’−イミノビス（プロピルアミン）が好適である。これらのアミノ基含有有機化合物は単独の状態では弱い抗菌性や抗かび性しか有していないにもかかわらず、これらを用いて得られた本発明のアミノ基含有粒子は優れた抗菌性および抗かび性を発現することができる。 From the viewpoint of antibacterial and antifungal properties, 3,3'-iminobis (propylamine) and N-methyl-3,3'-iminobis (propylamine) are preferred. Although these amino group-containing organic compounds have only weak antibacterial and antifungal properties when used alone, the amino group-containing particles of the present invention obtained using them have excellent antibacterial and antifungal properties. Can exhibit moldiness.
また、抗ウイルス性の観点からは、アミノ基含有有機化合物として、Ｎ−メチル−３，３’−イミノビス（プロピルアミン）、ラウリルイミノビスプロピルアミン、１，４−ビス（３−アミノプロピル）ピペラジンのような３級アミノ基を有するものを採用することがより望ましい。このようなアミノ基含有有機化合物を採用することでより優れた抗ウイルス性能を発現させることが可能である。３級アミノ基はアミノ基への電子供与が多く、このことが抗ウイルス性能向上に影響しているものと推定される。 From the viewpoint of antiviral properties, N-methyl-3,3′-iminobis (propylamine), lauryliminobispropylamine, 1,4-bis (3-aminopropyl) piperazine are used as the amino group-containing organic compound. It is more desirable to employ those having a tertiary amino group such as By adopting such an amino group-containing organic compound, it is possible to develop better antiviral performance. The tertiary amino group has a large amount of electron donation to the amino group, and it is presumed that this has an effect on improving the antiviral performance.
本発明のアミノ基含有粒子のアミノ基量、すなわち、アニオン交換容量としては、必要とする性能に応じて変化しうるが、一般的には０．１ｍｍｏｌ／ｇ以上が好ましく、０．５ｍｍｏｌ／ｇ以上であることがより好ましい。０．１ｍｍｏｌ／ｇ未満の場合には、アミノ基に由来する性能のいずれも得られない場合がある。各性能別に見ると、抗ウイルス性能については０．１ｍｍｏｌ／ｇであれば十分な性能が得られる。アニオン交換性能については０．５ｍｍｏｌ／ｇ以上であればアニオン交換粒子として実用的レベルである。また、原料となるニトリル基を含有する重合体からなる粒子の組成や架橋構造量にもよるが、後述する飽和吸湿率を発現させるにはアミノ基量を１．０ｍｍｏｌ／ｇ以上、飽和吸湿率差を発現させるにはアミノ基量を１．５ｍｍｏｌ／ｇ以上とすることが望ましい。また、上限については特に制限はないが、５ｍｍｏｌ／ｇ以下であれば、通常の反応条件の調整によって得ることが可能である。 The amino group content of the amino group-containing particles of the present invention, that is, the anion exchange capacity may vary depending on the required performance, but is generally preferably 0.1 mmol / g or more, and 0.5 mmol / g. More preferably. If it is less than 0.1 mmol / g, none of the performance derived from the amino group may be obtained. If it sees according to each performance, sufficient performance will be obtained if antiviral performance is 0.1 mmol / g. If the anion exchange performance is 0.5 mmol / g or more, it is a practical level as anion exchange particles. In addition, depending on the composition of the polymer particles containing nitrile groups as a raw material and the amount of the crosslinked structure, the amount of amino groups is 1.0 mmol / g or more and the saturated moisture absorption rate in order to develop the saturation moisture absorption rate described later. In order to express the difference, the amino group amount is desirably 1.5 mmol / g or more. Moreover, there is no restriction | limiting in particular about an upper limit, If it is 5 mmol / g or less, it can be obtained by adjustment of normal reaction conditions.
本発明のアミノ基含有粒子は、上述した特許文献１に代表されるカルボキシル基を利用する吸湿性粒子に匹敵する飽和吸湿率を有しており、広範囲にわたって飽和吸湿率を調節することが可能である。吸湿性粒子として使用する場合であれば、飽和吸湿率として２０℃６５％ＲＨの雰囲気下において、好ましくは１５質量％以上、より好ましくは２０質量％以上とすることが望ましい。 The amino group-containing particles of the present invention have a saturated moisture absorption rate comparable to the hygroscopic particles using the carboxyl group represented by Patent Document 1 described above, and the saturated moisture absorption rate can be adjusted over a wide range. is there. In the case of using as hygroscopic particles, the saturated moisture absorption rate is preferably 15% by mass or more, more preferably 20% by mass or more in an atmosphere of 20 ° C. and 65% RH.
また、本発明のアミノ基含有粒子は相対湿度によって飽和吸湿率が大きく変化することが大きな特徴の一つである。すなわち、本発明のアミノ基含有粒子においては、雰囲気湿度が高いときは吸湿し、雰囲気湿度が低いときは放湿するという調湿性を発現させることが可能である。調湿材として使用する場合、２０℃９５％ＲＨ雰囲気下と２０℃５０％ＲＨ雰囲気下での飽和吸湿率の差が５０パーセントポイント以上とすることが望ましい。 In addition, the amino group-containing particles of the present invention are one of the major features that the saturated moisture absorption rate varies greatly depending on the relative humidity. That is, in the amino group-containing particles of the present invention, it is possible to develop a humidity control property of absorbing moisture when the atmospheric humidity is high and releasing moisture when the atmospheric humidity is low. When used as a humidity control material, it is desirable that the difference in saturated moisture absorption between the 20 ° C. and 95% RH atmosphere and the 20 ° C. and 50% RH atmosphere be 50 percentage points or more.
上記のアミノ基量は、採用するアミノ基含有有機化合物の種類、すなわち、該化合物のアミノ基数および導入量により調節することができる。また、架橋構造量はアミノ基量に比例して増加する傾向となる。しかし、採用するアミノ基含有有機化合物の種類を選択することにより、架橋構造量とアミノ基量のバランスを調節することも可能である。例えば、１分子中に多くの２級あるいは３級アミノ基を有する化合物を用いれば、アミノ基量を多くしつつ、架橋構造を少なくすることができる。反対に、１分子中のアミノ基の数が少ない化合物を用いれば、アミノ基量を少なくしつつ、架橋構造を多くすることもできる。 The amount of the amino group can be adjusted by the type of the amino group-containing organic compound to be employed, that is, the number of amino groups and the amount of introduction of the compound. Further, the amount of the crosslinked structure tends to increase in proportion to the amount of amino groups. However, it is also possible to adjust the balance between the amount of the crosslinked structure and the amount of amino groups by selecting the type of amino group-containing organic compound to be employed. For example, if a compound having many secondary or tertiary amino groups in one molecule is used, the cross-linking structure can be reduced while increasing the amount of amino groups. On the other hand, if a compound having a small number of amino groups in one molecule is used, the cross-linking structure can be increased while reducing the amount of amino groups.
アミノ基含有有機化合物でニトリル基を含有する重合体からなる粒子を処理する方法としては、特に制限されるものではないが、アミノ基含有有機化合物の水溶液を用意し、ニトリル基を含有する重合体からなる粒子を該水溶液に浸漬、もしくは、ニトリル基を含有する重合体からなる粒子に該水溶液を噴霧する方法などが挙げられる。 A method for treating particles comprising a polymer containing a nitrile group with an amino group-containing organic compound is not particularly limited, but a polymer containing a nitrile group is prepared by preparing an aqueous solution of an amino group-containing organic compound. And a method of spraying the aqueous solution onto particles made of a polymer containing a nitrile group.
アミノ基含有有機化合物でニトリル基を含有する重合体からなる粒子を処理する条件としては、特に制限はなく、採用するアミノ基含有有機化合物とニトリル基を含有する重合体からなる粒子との反応性や所望のアミノ基量および架橋構造量、すなわちアニオン交換性能、飽和吸湿率、飽和吸湿率差などの必要とする性能を勘案し、適宜選定することができる。例えば、上述したニトリル基を含有する重合体からなる粒子をアミノ基含有有機化合物水溶液に浸漬する方法の場合であれば、アミノ基含有有機化合物水溶液の濃度を、ニトリル基を含有する重合体からなる粒子に対し１質量％以上となるようにした場合、上述した０．１ｍｍｏｌ／ｇ以上のアミノ基量が得られやすい。 There are no particular restrictions on the conditions for treating particles comprising a polymer containing a nitrile group with an amino group-containing organic compound, and the reactivity between the amino group-containing organic compound employed and particles comprising a polymer containing a nitrile group is not limited. Or a desired amino group amount and a crosslinked structure amount, that is, an anion exchange performance, a saturated moisture absorption rate, a saturated moisture absorption rate, and other necessary performances. For example, in the case of the method of immersing particles composed of a polymer containing a nitrile group in an amino group-containing organic compound aqueous solution, the concentration of the amino group-containing organic compound aqueous solution is made of a polymer containing a nitrile group. When the amount is 1% by mass or more based on the particles, the above-described amino group amount of 0.1 mmol / g or more is easily obtained.
また、反応温度としては、使用するアミノ基含有有機化合物の種類によって程度の差はあるが、低すぎる場合には、反応速度が遅くなって長時間の反応時間が必要となり、高すぎる場合には、アミノ基含有有機化合物の分解が懸念される。そのため、好ましくは５０〜１５０℃、さらに好ましくは８０〜１５０℃で反応させた場合好ましい結果を得る場合が多い。反応時間については、反応温度等にもよるが通常３０分〜４８時間ぐらいで目的とする量の架橋構造とアミノ基を導入することができる。特に、本発明に採用するアミノ基含有有機化合物において、アミノ基間を炭素数が３以上のアルキレン基で結合した構造を有するものの場合、３０分〜４時間程度で目的とする量の架橋構造とアミノ基を導入することができる。 In addition, the reaction temperature varies depending on the type of amino group-containing organic compound used, but if it is too low, the reaction rate becomes slow and a long reaction time is required. There is a concern about the decomposition of the amino group-containing organic compound. Therefore, preferable results are often obtained when the reaction is preferably carried out at 50 to 150 ° C, more preferably 80 to 150 ° C. Regarding the reaction time, although depending on the reaction temperature and the like, the desired amount of the crosslinked structure and amino group can be introduced usually in about 30 minutes to 48 hours. In particular, in the amino group-containing organic compound employed in the present invention, when the amino group has a structure in which the amino groups are bonded by an alkylene group having 3 or more carbon atoms, the desired amount of the crosslinked structure is about 30 minutes to 4 hours. An amino group can be introduced.
本発明のアミノ基含有粒子の粒子径には特に限定はなく、利用される用途に応じて適宜選択することができる。例えば、吸湿速度を速くしたい場合、粒子表面積を大きくとる必要があるため粒子径を１０μｍ以下とすることが好ましく、さらに好ましくは１μｍ以下した場合良好な結果が得られる。また塗料等への添加剤として使用した時に、被添加物の外観・物性に影響を与えないという点からは粒子径が１０μｍ以下であるものが好ましい。一方、樹脂等へ添加する場合は取り扱い、混練の点から１０〜１００μｍが好ましいなど用途によって使い分けることができる。 The particle diameter of the amino group-containing particles of the present invention is not particularly limited and can be appropriately selected according to the application to be used. For example, when it is desired to increase the moisture absorption rate, it is necessary to increase the particle surface area, so that the particle diameter is preferably 10 μm or less, and more preferably, 1 μm or less provides good results. Also, those having a particle size of 10 μm or less are preferred in that they do not affect the appearance and physical properties of the additive when used as an additive to paints and the like. On the other hand, when adding to resin etc., 10-100 micrometers is preferable from the point of handling and kneading | mixing, and it can use properly.
本発明のアミノ基含有粒子は、粒子状であるため、樹脂成形体、プラスチックフォーム、フィルム、塗膜、紙、不織布、合成繊維などのさまざまな形態の材料の製造時に添加したり、製造後のこれらの材料にバインダーなど用いて固着させたりするなど、さまざまな方法で各種材料に適用することができる。 Since the amino group-containing particles of the present invention are in the form of particles, they can be added during the production of various forms of materials such as resin molded bodies, plastic foams, films, coating films, paper, nonwoven fabrics, synthetic fibers, and the like. It can be applied to various materials by various methods such as fixing to these materials using a binder.
本発明のアミノ基含有粒子を適用した材料は、アニオン交換、吸湿、抗菌、抗かび、抗ウイルスなどの機能を有する機能性製品として利用することができる。具体的には、アニオン交換性能を利用した、水の軟化・脱塩用の素材、ケミカルフィルター、たばこフィルター、浄水器用吸着材、原子力発電所用イオン交換濾過材、消臭材、あるいは、吸湿性能を利用した、結露防止素材、吸放湿素材（建材、壁紙等）、環境の調湿、調温素材、あるいは押入れ、地下室、床下、浴室等の乾燥素材、水分を非常に嫌う電子材料等の被覆素材の一部、さらには、抗菌、抗かび、抗ウイルスを利用した各種フィルター、マスク、タオル、靴下、インソール、壁紙など、さまざまな分野において有用な機能性製品として利用することができる。 The material to which the amino group-containing particles of the present invention are applied can be used as a functional product having functions such as anion exchange, moisture absorption, antibacterial, antifungal, and antiviral. Specifically, water softening and desalting materials, chemical filters, cigarette filters, water purifier adsorbents, nuclear power plant ion exchange filter materials, deodorant materials, or moisture absorption performance using anion exchange performance. Condensation prevention materials, moisture absorption / release materials (building materials, wallpaper, etc.), environmental humidity control, temperature control materials, dry materials such as closets, basements, underfloors, bathrooms, etc. It can be used as a functional product useful in various fields such as a part of materials, and various filters using antibacterial, antifungal and antiviral, masks, towels, socks, insoles and wallpaper.
以下、実施例により本発明を具体的に説明する。本発明は、これらの実施例の記載によってその範囲を何等限定されるものではない。実施例中の部及び百分率は、断りのない限り質量基準で示す。なお、各測定値は以下の方法により求めた。 Hereinafter, the present invention will be described specifically by way of examples. The scope of the present invention is not limited in any way by the description of these examples. Unless otherwise indicated, parts and percentages in the examples are based on mass. In addition, each measured value was calculated | required with the following method.
（１）アミノ基量（アニオン交換容量）
充分に乾燥した試料約０．５ｇを精秤し（Ｘ［ｇ］）、イオン交換水中で分散させる。この分散液に、０．１Ｎ塩酸標準液を滴下し、滴定曲線を作成した。滴定曲線より求めた０．１Ｎ塩酸標準水溶液の滴定量をＹ［ｍｌ］、ファクターをｆ[HCl]として、次式により、アミノ基量を算出した。
アミノ基量［ｍｍｏｌ／ｇ］＝（０．１×Ｙ×ｆ〔HCl〕）／ Ｘ
(1) Amino group content (anion exchange capacity)
About 0.5 g of a sufficiently dried sample is precisely weighed (X [g]) and dispersed in ion-exchanged water. To this dispersion, 0.1N hydrochloric acid standard solution was dropped to prepare a titration curve. The amount of amino group was calculated by the following formula, where the titration amount of 0.1N hydrochloric acid standard aqueous solution obtained from the titration curve was Y [ml] and the factor was f [HCl].
Amino group amount [mmol / g] = (0.1 × Y × f [HCl]) / X
（２）飽和吸湿率および飽和吸湿率差
充分に乾燥した試料約５ｇを精秤する（Ｗ１［ｇ］）。該試料を２０℃、所定の相対湿度（５０％ＲＨ、６５％ＲＨ及び９５％ＲＨ）下で２４時間静置する。このようにして吸湿させた試料の質量を測定する（Ｗ２［ｇ］）。以上の測定結果から、次式によって各相対湿度における飽和吸湿率を算出した。
飽和吸湿率［％］＝（Ｗ２−Ｗ１）／Ｗ１×１００
なお、飽和吸湿率差は、以上のようにして求めた２０℃５０％ＲＨの飽和吸湿率と２０℃９５％ＲＨの飽和吸湿率の差である。
(2) Saturated moisture absorption and saturated moisture absorption difference Weigh about 5 g of a sufficiently dried sample (W1 [g]). The sample is allowed to stand for 24 hours at 20 ° C. and a predetermined relative humidity (50% RH, 65% RH and 95% RH). The mass of the sample thus absorbed is measured (W2 [g]). From the above measurement results, the saturated moisture absorption rate at each relative humidity was calculated by the following equation.
Saturated moisture absorption [%] = (W2-W1) / W1 × 100
The difference in saturated moisture absorption is the difference between the saturated moisture absorption at 20 ° C. and 50% RH and the saturation moisture absorption at 20 ° C. and 95% RH determined as described above.
（３）平均粒子径
島津製作所製レーザー回折式粒度分布測定装置「ＳＡＬＤ−２００Ｖ」を使用して水を分散媒として測定し、体積基準で表した粒子径分布から、平均粒子径［μｍ］を求めた。
(3) Average particle diameter Using a laser diffraction particle size distribution measuring device “SALD-200V” manufactured by Shimadzu Corporation, water is measured as a dispersion medium, and the average particle diameter [μm] is calculated from the particle diameter distribution expressed by volume. Asked.
（実施例１）
メタクリル酸／p-スチレンスルホン酸ソーダ＝７０／３０の水溶性重合体３００部、及び硫酸ナトリウム３０部を６５９５部の水に溶解し、攪拌機付き重合槽に仕込んだ。次に、アクリロニトリル２７００部及びアクリル酸メチル３００部に、２、２’アゾビス−（２,４−ジメチルバレロニトリル）１５部を溶解して重合槽に仕込み６０℃、２時間重合を行うことにより、平均粒子径７８μｍのニトリル基を含有する重合体からなる原料粒子Ａを得た。
Example 1
300 parts of a water-soluble polymer of methacrylic acid / p-sodium styrenesulfonate = 70/30 and 30 parts of sodium sulfate were dissolved in 6595 parts of water and charged into a polymerization tank equipped with a stirrer. Next, 15 parts of 2,2′azobis- (2,4-dimethylvaleronitrile) is dissolved in 2700 parts of acrylonitrile and 300 parts of methyl acrylate, charged in a polymerization tank, and polymerized at 60 ° C. for 2 hours. Raw material particles A made of a polymer containing a nitrile group having an average particle diameter of 78 μm were obtained.
原料粒子Ａ１０部を、該粒子に対して３００％のＮ−メチル−３，３’−イミノビス（プロピルアミン）を含む水溶液２００部に浸漬し、処理温度８５℃、処理時間２時間で処理、水洗、乾燥し、実施例１のアミノ基含有粒子を得た。該粒子の評価結果を表１に示す。 10 parts of raw material particles A were immersed in 200 parts of an aqueous solution containing 300% N-methyl-3,3′-iminobis (propylamine) with respect to the particles, treated at a treatment temperature of 85 ° C. for a treatment time of 2 hours, and washed with water. Then, the amino group-containing particles of Example 1 were obtained. The evaluation results of the particles are shown in Table 1.
（実施例２、３、比較例１〜３）
実施例１において、表１に示す原料および条件に変更して粒子を作成し、評価を行った。評価結果を表１に示す。
(Examples 2 and 3 and Comparative Examples 1 to 3 )
In Example 1, particles were prepared by changing to the raw materials and conditions shown in Table 1 and evaluated. The evaluation results are shown in Table 1.
（実施例４）
アクリロニトリル４４０部、アクリル酸メチル５０部、乳化剤としてドデシルベンゼンスルホン酸ソーダ１６部、及び水１１８１部をオートクレーブ内に仕込み、更に重合開始剤としてジ−ｔ−ブチルパーオキサイドを単量体全体に対して０．５％添加した後、密閉し、次いで攪拌下において１３０℃で、２３分間重合を行うことにより、平均粒子径２００ｎｍのニトリル基を含有する重合体からなる原料粒子Ｂの水分散体を得た。
(Example 4 )
440 parts of acrylonitrile, 50 parts of methyl acrylate, 16 parts of sodium dodecylbenzenesulfonate as an emulsifier, and 1181 parts of water are charged into an autoclave, and di-t-butyl peroxide is added to the whole monomer as a polymerization initiator. After adding 0.5%, the mixture is sealed and then polymerized at 130 ° C. under stirring for 23 minutes to obtain an aqueous dispersion of raw material particles B made of a polymer containing a nitrile group having an average particle size of 200 nm. It was.
原料粒子Ｂの水分散体に固形分が１０％となるように水を加えて得た水分散液１００部に、該粒子に対して３００％のＮ−メチル−３，３’−イミノビス（プロピルアミン）を含む水溶液１００部を加え、処理温度１１５℃、処理時間２時間で処理し、実施例４のアミノ基含有粒子の水分散体を得た。該粒子の評価結果を表１に示す。なお、該粒子の評価については、得られた水分散体にメチルアルコールを加えて粒子を沈降させ、ろ紙でろ過後、充分に洗浄、乾燥したものを用いて評価を行った。
To 100 parts of an aqueous dispersion obtained by adding water to the aqueous dispersion of the raw material particles B so that the solid content is 10%, 300% of N-methyl-3,3′-iminobis (propyl) is added to the particles. 100 parts of an aqueous solution containing amine) was added, and the mixture was treated at a treatment temperature of 115 ° C. for a treatment time of 2 hours to obtain an aqueous dispersion of amino group-containing particles of Example 4 . The evaluation results of the particles are shown in Table 1. In addition, about evaluation of this particle | grain, methyl alcohol was added to the obtained water dispersion, particle | grains were settled, and it evaluated using what was fully washed and dried after filtering with a filter paper.
実施例１〜４では、良好なアニオン交換性能、吸湿性能を有するアミノ基含有繊粒子が得られた。特に、アミノ基含有有機化合物としてアミノ基間を炭素数が３以上のアルキレン基で結合した構造を有するものを採用した実施例２および３は、比較例１に比べて短い反応時間でも同等の量のアミノ基が導入され、着色も少ないものであった。また、比較例２および３では採用したアミノ基含有有機化合物のアミノ基数が２以下であり、ニトリル基との反応でほとんどのアミノ基が消費されたため、本発明に比べ、性能の低いものとなったと考えられる。 In Examples 1 to 4 , amino group-containing fine particles having good anion exchange performance and hygroscopic performance were obtained. In particular, Examples 2 and 3 adopting an amino group-containing organic compound having a structure in which an amino group is bonded with an alkylene group having 3 or more carbon atoms are equivalent in an amount equivalent to that of Comparative Example 1 even in a shorter reaction time. The amino group was introduced, and coloring was also small. In Comparative Examples 2 and 3 , the number of amino groups of the amino group-containing organic compound employed was 2 or less, and most of the amino groups were consumed in the reaction with the nitrile group, so that the performance was lower than that of the present invention. It is thought.
Claims (6)
The functional product containing the amino group containing particle | grains in any one of Claims 1-4 .
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